Near Infrared-Activated Dye-Linked ZnO Nanoparticles Release Reactive Oxygen Species for Potential Use in Photodynamic Therapy.

Novel dye-linked zinc oxide nanoparticles (NPs) hold potential as photosensitizers for biomedical applications due to their excellent thermal- and photo-stability. The particles produced reactive oxygen species (ROS) upon irradiation with 850 nm near infrared (NIR) light in a concentration- and time-dependent manner. Upon irradiation, ROS detected in vitro in human umbilical vein endothelial cells (HUVEC) and human carcinoma MCF7 cells positively correlated with particle concentration and interestingly, ROS detected in MCF7 was higher than in HUVEC. Preferential cytotoxicity was also exhibited by the NPs as cell killing was higher in MCF7 than in HUVEC. In the absence of irradiation, dye-linked ZnO particles minimally affected the viability of cell (HUVEC) at low concentrations (<30 µg/mL), but viability significantly decreased at higher particle concentrations, suggesting a need for particle surface modification with poly (ethylene glycol) (PEG) for improved biocompatibility. The presence of PEG on particles after dialysis was indicated by an increase in size, an increase in zeta potential towards neutral, and spectroscopy results. Cell viability was improved in the absence of irradiation when cells were exposed to PEG-coated, dye-linked ZnO particles compared to non-surface modified particles. The present study shows that there is potential for biological application of dye-linked ZnO particles in photodynamic therapy.

Metal Hydroxide/Polymer Textiles for Decontamination of Toxic Organophosphates: An Extensive Study of Wettability, Catalytic Activity, and the Effects of Aggregation.

Electrospun nanofibers (NFs) incorporated with catalytically active components have gained significant interest in chemical protective clothing. This is because of the desirable properties of the NFs combined with decontamination capability of the active component. Here, a series of metal hydroxide catalysts Ti(OH)x, Zr(OH)4, and Ce(OH)4 were incorporated into three different polymer NF systems. These new polymer/metal hydroxide composite NFs were then evaluated for their catalytic activity against a nerve agent simulant. Two methods were utilized to incorporate the metal hydroxides into the NFs. Method one used direct incorporation of Ti(OH)x, Zr(OH)4, and Ce(OH)4 catalysts, whereas method two employed incorporation of Ti(OH)x via a precursor molecule. Composite NFs prepared via method one resulted in greatly improved reaction rates over the respective pure metal hydroxides due to reduced aggregation of catalysts, with polymer/Ce(OH)4 composite NFs having the fastest reaction rates out of method one materials. Interestingly, composite samples prepared by method two yielded the fastest reaction rates overall. This is because of the homogeneous distribution of the metal hydroxide catalyst throughout the NF. This homogeneous distribution created a hydroxyl-decorated NF surface with a greater number of exposed active sites for catalysis. The hydroxyl-decorated NF surface also resulted in an unexpected highly wettable composite NF, which also was found to contribute to the observed reaction rates. These results are not only promising for applications in chemical protective clothing but also show great potential for application in areas which need highly wettable membrane materials. This includes areas such as separators, antifouling membranes, and certain medical applications.

Chemical Protective Textiles of UiO-66-Integrated PVDF Composite Fibers with Rapid Heterogeneous Decontamination of Toxic Organophosphates.

Metal-organic frameworks (MOFs) are a new and growing area of materials with high porosity and customizability. UiO-66, a zirconium-based MOF, has shown much interest to the military because of the ability of the MOF to catalytically decontaminate chemical warfare agents (CWAs). Unfortunately, the applications for MOFs are limited because of their powder form, which is difficult to incorporate into protective clothing. As a result, a new area of research has developed to functionalize fabrics with MOFs to make a wearable multifunctional fabric that retains the desired properties of the MOF. In this work, UiO-66 was incorporated into poly(vinylidene) fluoride/Ti(OH)4 composite fabric using electrospinning and evaluated for its use in chemical protective clothing. The base triethanolamine (TEA) was added to the composite fabric to create a self-buffering system that would allow for catalytic decontamination of CWAs without the need for a buffer solution. The fabrics were tested against the simulants methyl-paraoxon (dimethyl (4-nitrophenyl) phosphate, DMNP), diisopropyl fluorophosphate (DFP), and the nerve agent soman (GD). The results show that all of the samples have high moisture vapor transport and filtration efficiency, which are desirable for protective clothing. The incorporation of TEA decreased air permeation of the fabric, but increased the catalytic activity of the composite fabric against DMNP and DFP. Samples with and without TEA have rapid half-lives ( t1/2) as short as 35 min against GD agent. These new catalytically active self-buffering multifunctional fabrics have great potential for application in chemical protective clothings.

Toxic Organophosphate Hydrolysis Using Nanofiber-Templated UiO-66-NH2 Metal-Organic Framework Polycrystalline Cylinders.

Metal organic frameworks (MOFs), the UiO series in particular, have attracted much attention because of the high surface area and ability to capture and decontaminate chemical warfare agents. Much work has been done on incorporating these MOFs into or onto textile materials while retaining the desirable properties of the MOF. Many different techniques have been explored to achieve this. Atomic layer deposition (ALD) of TiO2 followed by solvothermal synthesis of MOF has become one of the most adaptable techniques for growing MOFs on the surface of many different polymer fabric materials. However, little work has been done with using this technique on polymer composite materials. In this work, UiO-66-NH2 was grown onto the surface of poly(methyl methacrylate) (PMMA)/Ti(OH)4 and poly(vinylidene fluoride) (PVDF)/Ti(OH)4 composite fibers by first modifying the surface with ALD of TiO2 (@TiO2) followed by solvothermal synthesis of MOF (@MOF). The catalytic activity of these materials was then evaluated using the simulant paraoxon-methyl (DMNP). These new MOF-functionalized composite fabrics were compared to polyamide-6 (PA-6)@TiO2@MOF- and polypropylene (PP)@TiO2@MOF-functionalized fabrics. PMMA/Ti(OH)4@TiO2@MOF fibers resulted in unique hollowed fibers with high surface area of 264 m2/g and fast catalytic activity. The catalytic activity of these samples was found to be related to the active MOF mass fraction on the MOF-functionalized composite fabric, with the hollowed PMMA/Ti(OH)4@TiO2@MOF having the highest weight percent of active MOF and a DMNP t1/2 of 26 min followed by PA-6@TiO2@MOF with 45 min, PVDF/Ti(OH)4@TiO2@MOF with 61 min, and PP@TiO2@MOF with 83 min.

Facile Synthesis of Fluorescent Conjugated Polyelectrolytes Using Polydentate Sulfonate as Highly Selective and Sensitive Copper(II) Sensors.

Fluorescent conjugated polyelectrolytes represent an exciting area of research into new chemosensors. By virtue of their rapid electron and energy transfer paths, these highly correlated, one-dimensional systems have been depicted as "molecular wires" and show "million-fold" sensitivity compared to monomolecular sensor analogs. In this paper, a novel polyelectrolyte sensor, the ttp-PPESO3, has been designed by incorporating terpyridine and sulfonate functional groups into the polyelectrolyte. This specifically tailored sensor has displayed remarkable quenching response toward copper(II) with a detection limit of 14.7 nM (0.93 ppb). It is capable of selectively screening copper without interference from 12 common cations. Molecular modeling suggests that binding occurs through a coordination interaction of the terpyridine and sulfonate. The additional multidentate nature from the sulfonate offers extraordinary chelating ability to the analyte. We anticipate that this unique binding mode will provide insight for the design of future more sensitive and selective systems.

Pentiptycene-Derived Fluorescence Turn-Off Polymer Chemosensor for Copper(II) Cation with High Selectivity and Sensitivity.

Fluorescent conjugated polymers (FCPs) have been explored for selective detection of metal cations with ultra-sensitivity in environmental and biological systems. Herein, a new FCP sensor, tmeda-PPpETE (poly[(pentiptycene ethynylene)-alt-(thienylene ethynylene)] with a N,N,N'-trimethylethylenediamino receptor), has been designed and synthesized via Sonogashira cross-coupling reaction with the goal of improving solid state polymer sensor development. The polymer was found to be emissive at λmax ~ 459 nm under UV radiation with a quantum yield of 0.119 at room temperature in THF solution. By incorporating diamino receptors and pentiptycene groups into the poly[(phenylene ethynylene)-(thiophene ethynylene)] (PPETE) backbone, the polymer showed an improved turn-off response towards copper(II) cation, with more than 99% quenching in fluorescence emission. It is capable of discriminating copper(II) cation from sixteen common cations, with a detection limit of 16.5 nM (1.04 ppb).

METAL-CONTAINING CONJUGATED POLYMERS AS FLUORESCENT CHEMOSENSORS IN THE DETECTION OF TOXICANTS.

Fluorescent conjugated polymers have received a great deal of recent interest due to their ability to act as chemosensors to detect various chemical species in both environmental and biological systems with sensitivity and selectivity. Examples from the literature include polymer chemosensors that operate on either fluorescence "turn-on" or "turn-off" as mechanisms of sensor response. These responses can be related to either photoinduced electron transfer or electronic energy transfer mechanisms. Recently, a series of metal-containing polymers or metallopolymers have been explored by various research groups for their use as chemosensors. In many cases, these metallopolymers have been shown to be more sensitive and selective for specific chemical species. This review focuses on fluorescent conjugated polymers as chemosensors, with a specific concentration on recent advances in metallopolymer chemosensors.

Electrically conducting polymers as templating interfaces for fabrication of copper nanotubes.

Submicrometer tubes have been fabricated by a polymer-based template approach using electroless deposition. The copper was deposited on polystyrene fibers functionalized with an interfacial electrically conducting polyaniline thin film layer. Thermal degradation of the functionalized fiber templates resulted in copper tubes of diameter 1600 ± 50 nm with wall thicknesses ranging between 100 and 200 nm. The morphology and elemental analysis of copper coaxial fibers was analyzed using SEM and EDS. Electrical properties were analyzed using FTIR and PXRD was used to study crystal structure of copper nanotubes.

The role of intermolecular interactions in solid state fluorescent conjugated polymer chemosensors.

A functionalized fluorescent conjugated polymer, tolylterpyridine poly(p-phenyleneethynylene-thienyleneethynylene (ttp-PPETE), was designed and synthesized to detect trace amounts of toxic transition metal pollutants in ground water. Photophysical studies in tetrahydrofuran (THF) successfully demonstrated this polymer as a selective and sensitive chemosensor for Ni(2+) and Co(2+) in aqueous solution. Solid state composites of these chemosensors have now been prepared which can be modified to provide for inexpensive and portable field based chemical detection. A solid composite of ttp-PPETE, blended with poly (methyl methacrylate) shows UV-vis absorption and fluorescence emission spectra which are red- shifted when compared to solution phase spectra, suggesting an increase in conjugation in the solid state. An additional absorption peak, not present in solution, is also observed in the solid state. The presence of this new peak provides evidence of interacting FCP chains in the solid state. Concentration dependent experiments were done on the solid composite showing red-shifted emission peaks accompanied by a significant reduction in the fluorescent quantum yield. These observations are consistent with the formation of aggregated polymer species in the solid state. Intermolecular interactions of this type can be manipulated in the design of sensitive and selective solid state fluorescent conjugated polymer sensors.

Polyacrylonitrile-based carbonized fibers and metal-carbonized fiber nanocomposites for thermal transport.

This work examines the fabrication and thermal analysis of metal-carbon composite fibers prepared via an electrospinning process. The metal-carbon composite fibers of silver, copper, gold, and nickel were prepared by electrospinning of a composite solution of polyacrylonitrile (PAN) and metal precursor followed by heat treatment in air, nitrogen to 1000 degrees C and in 6% H2, respectively. Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Energy dispersive spectroscopy (EDS) and Scanning thermal microscopy (SThM) were applied to characterize the metal-carbon fibers. TEM analysis showed a relatively uniform, contact-free distribution of the nanoparticles on the surface of the carbon fibers with size range of 3 nm-10 nm. Thermal analysis data showed an enhancement in the thermal conductivity of the nanomaterials when compared with the model PAN-based carbonized fibers. This was attributed to the incorporation of metal nanoparticles in the fiber matrix and on the surface.

Synthesis and optical properties of co-doped ZnO submicrometer tubes from electrospun fiber templates.

Submicrometer ZnO tubes have been synthesized by a polymer based template approach using sol-gel deposition. Zinc acetate, a precursor to ZnO, was deposited on catalytically active electrospun polycarbonate fibers approximately 250+/-100 nm in diameter. Thermal degradation of the core fibers resulted in the oxidation of zinc acetate to produce ZnO nanotubes with diameters of approximately 500+/-100 nm and an average wall thickness of approximately 100+/-50 nm. Scanning electron microscopy (SEM), Energy dispersive spectroscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and UV-visible spectroscopy were used to characterize the composition, structure, and morphology of the tubes. Powder X-ray diffraction results showed that a wurtzite crystalline phase was obtained. The UV-visible absorption spectrum was red-shifted by 25 nm due to narrowing of the ZnO band gap (approximately 3.22 eV) as a result of Co doping. Similarly, green band emission was not observed in the emission spectrum, while emission lifetime was determined to be 620 ps from photoluminescence studies.

Competition between energy transfer quenching and chelation enhanced fluorescence in a Cu (II) coordinated conjugated polymer system.

An investigation of the mechanism of the fluorescence quenching by Cu(2+) for a conjugated polymer system initially designed as a fluorescence "turn-on" chemosensor based on chelation enhanced fluorescence (CHEF) is described in this paper. Unlike all other metal cations tested, the polymer/Cu(2+) hybrid system with a 1:1 ratio between the receptor and Cu(2+) has only weak fluorescence with lambda(max) = 490 nm and a quantum yield of 0.004 in THF at room temperature. In solvent glasses at 77 K the fluorescence remained quenched suggesting that the quenching mechanism was due to energy transfer between the Cu(2+) and the conjugated polymer backbone. The energy transfer quenching competes effectively with the electron transfer involved in the CHEF resulting in a more selective chemosensory system.

Fabrication and thermal analysis of submicron silver tubes prepared from electrospun fiber templates.

Submicron silver tubes have been synthesized by a polymer-based template approach. Two different approaches to metallization, electroless deposition and exchange plating, were evaluated within the template approach. Silver films with average thickness approximately 50-100 nm were deposited on polycarbonate fibers approximately 400 nm in diameter by each technique, resulting in tubes with a diameter between 450 and 500 nm after thermal degradation of core fibers. These nanomaterials were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and scanning thermal microscopy. The thermal conductivity of the silver submicron tubes was found to differ depending on the method of preparation, with tubes from electroless plating possessing relative thermal conductivity values that were 1 order of magnitude higher than that from exchange plating, 3000 W/m x K and 660 W/m x K, respectively. Interestingly, these results indicate that silver submicron tubes possess higher thermal conductivity than the bulk metal. This observation is discussed in the context of the continuous conduction path of the tubes and their high surface area-to-volume ratio.

Enhanced conductivity of thin film polyaniline by self-assembled transition metal complexes.

In a recent study, the transition metal complex, cis-dichlorobis(2-,2'-dipyridyl)ruthenium (II) (Ru(bpy)2Cl2), and the macrocycle Ru(TPP)CO (TPP:- tetraphenylporphine) were bound to pyridine terminated self-assembled monolayers on quartz. Following modification of the quartz surface with metal complexes, the conducting polymer polyaniline was deposited via in situ polymerization. The sheet conductivity (as measured by the four-probe method) of the resulting polyaniline films deposited onto Ru(bpy)2Cl2 and Ru(TPP)CO surfaces was significantly enhanced relative to films deposited onto unmodified quartz. It is postulated that either the macrocycle or the transition metal complex-modified surface interacts with the conducting polymer as it is forming, resulting in a more ordered expanded coil conformation for the polymer. The net result of such an interaction is a thin film possessing significantly greater electrical conductivity.

Preparation of submicron polypyrrole/poly(methyl methacrylate) coaxial fibers and conversion to polypyrrole tubes and carbon tubes.

In an effort to prepare electrically conductive nanofiber and nanotube materials, polypyrrole/poly(methyl methacrylate) coaxial fibers have been prepared using polymer fibers produced from an electrospinning process. Poly(methyl methacrylate) (PMMA) fibers with an average diameter of 230 nm were initially fabricated by electrospinning as core materials. The PMMA fibers were subsequently coated as templates with a thin layer of polypyrrole (PPy) by in-situ deposition of the conducting polymer from aqueous solution. Hollow PPy tubes were produced by dissolution of the PMMA core from PPy/PMMA coaxial fibers. High-temperature (1000 degrees C) treatment under inert atmosphere converted PPy/PMMA coaxial fibers into carbon tubes by complete decomposition of PMMA fiber core and carbonization of the PPy wall. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and FT-IR spectroscopy confirmed the formation of the PPy/PMMA coaxial fibers, PPy tubes, and carbon tubes.

A highly selective and sensitive inorganic/organic hybrid polymer fluorescence "turn-on" chemosensory system for iron cations.

A polymer-based fluorescence "turn-on" chemosensor is demonstrated with high sensitivity and selectivity toward Fe2+ cations. This system is an inorganic/organic hybrid system in which Cu2+ is coordinated at the receptor site of a conjugated polymer sensor. The unique quenching behavior of the Cu2+ toward this conjugated polymer was used to lower the initial fluorescence intensity of the sensory system. This results in a highly sensitive and also selective sensory system toward Fe2+ as compared to other related divalent transition-metal cations in solution.

Studies of photoinduced electron transfer and energy migration in a conjugated polymer system for fluorescence "turn-on" chemosensor applications.

A series of poly[p-(phenyleneethynylene)-alt-(thienyleneethynylene)] (PPETE) polymers with variable percent loadings of the N,N,N'-trimethylethylenediamino group on the polymer backbone were synthesized and fully characterized. Photophysical studies show that changes in the loading of the amino group receptor on the backbone do not affect the polymer electronic structure in either the ground or excited states. The fluorescence quantum yields were found to be directly related to the loading of the amino groups and can be modeled by a Stern-Volmer type relationship. Photophysical studies related the total quenching efficiency to the inherent rate of photoinduced electron transfer (PET), the lifetime of the exciton, the rate of excitation energy migration along the polymer backbone, and the total loading of the receptor on the polymer. The role of the loading dependence on the application of these polymers as fluorescence "turn-on" sensors for toxic metal cations in dilute solution was also studied. Results showed that the fluorescence enhancement upon binding various cations was maintained even when the amino receptor loading along the polymer backbone was reduced.

Sub-micrometer-sized metal tubes from electrospun fiber templates.

Metallic tubes have been synthesized by a polymer-based template approach using electroless deposition. Gold, copper, and nickel were deposited as thin films on sub-micrometer polymer fibers which ranged in diameter from approximately 160 to 400 nm. After thermal degradation of the template fibers at 300 and 650 degrees C, tubes between 450 and 730 nm were obtained with wall thicknesses of 50-150 nm. Characterization by scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and powder X-ray diffraction indicate that the tubes have a face-centered cubic structure with [111] preferred orientation for all of the metals investigated and that the tube walls are polycrystalline, composed of nanoparticles, ranging in size from 5.0 to 25.0 nm.

Photophysical properties of Ru(II) bipyridyl complexes containing hemilabile phosphine-ether ligands.

Emission and absorbance spectra, along with low-temperature excited-state lifetimes, were obtained for the hemilabile complexes, [Ru(bpy)2L](PF6)2 [L = (2-methoxyphenyl)diphenylphosphine (RuPOMe) (1) and (2-ethoxyphenyl)diphenylphosphine (RuPOEt) (2)] in solid 4:1 ethanol/methanol solution. Spectral data were evaluated with ground-state reduction potentials using Lever parameters. Lifetime data for these complexes were collected from 77 to 160 K, and the rate constant for the combined radiative and nonradiative decay process, k, the thermally activated process prefactor, k'(0), the rate constant for the MLCT --> d-d transition, k', and the activation energy, DeltaE', were calculated from a plot of ln(1/tau) versus 1/T for both (1) and (2). The low-temperature luminescence lifetimes of (1) were observed to decrease with increases in water concentration. The photophysical and kinetic data of (1) and (2) are compared to literature data for [Ru(bpy)3](PF6)2. The emission maxima of (1) and (2) are blue-shifted relative to [Ru(bpy)3](PF6)2 due to the presence of the strong-field phosphine ligand, which enhances pi back-bonding to the bipyridyl ligands. The thermal activation energy, DeltaE', is significantly larger for [Ru(bpy)3](PF6)2 than for (1) and (2) resulting in a faster MLCT --> d-d transition for (1) and (2). These results are discussed in the context of radiationless decay through thermally activated ligand-field states on the metal complex.

New structures in the bipyridine-copper(II) nitrate-methanol system: [(bpy)(2)Cu(NO(3))]NO(3) x CH(3)OH and [(bpy)(2)Cu(NO(3))]NO(3).

Reaction of 2,2'-bipyridine (bpy) and copper(II) nitrate in methanol results in two complexes, namely light-blue bis(2,2'-bipyridine)nitratocopper(II) nitrate methanol solvate, [Cu(NO(3))(C(10)H(8)N(2))(2)]NO(3) x CH(3)OH, (I), which is unstable in air, and the product of its decomposition, catena-poly[[[bis(2,2'-bipyridine)copper(II)]-mu-nitrato-O:O'] nitrate], [[Cu(NO(3))(C(10)H(8)N(2))(2)]NO(3)](n), (II). The crystal structures of both compounds were determined from one crystal at room temperature. Later, the structure of (I) was redetermined at low temperature. In (I) and (II), the Cu atom is coordinated by two bpy and one or two nitrate ions, respectively. The second nitrate ion in (I), along with the methanol solvent molecule, is found in the outer coordination sphere, not bonded to Cu. The nitrate in (I) is chelating, while in (II), it bridges (bpy)(2)Cu complexes, forming a one-dimensional chain structure. The Cu cation in (II) lies on a twofold axis and the uncoordinated NO(3)(-) ion is located close to a twofold axis and is therefore disordered. Compound (I) converts into (II) upon loss of solvent.